Bioconversion of Hemicelluloses into Hydrogen

Bioconversion of Hemicellulosesinto Hydrogen

Janak Raj Khatiwada, Sarita Shrestha, Hem Kanta Sharma,and Wensheng Qin

Abstract

Hydrogen is a promising alternative to fossil fuelsbecause of its environment-friendly characteristics. Ithas been used widely in varied sectors such as chemicalproduction, electronic devices, food industries, desulfur-ization of crude oil, and steel industries. Due to itsincreasing use and demand, it is essential to develop acheaper and energy-efficient source of hydrogen produc-tion. This review synthesizes and discusses variousaspects of hydrogen production methods and processes,the challenges, and economic perspective for sustainableproduction of biohydrogen. Compared to electrolysis,thermochemical and electrochemical processes, the bio-hydrogen production is environment friendly and energyefficient. Various factors such as feedstock, pH, temper-ature, partial pressure of hydrogen, and hydraulic reten-tion time are responsible for the biological process andyield of biological hydrogen production. This reviewsuggests that lignocellulosic biomass is commonly avail-able, cheaper and eco-friendly source of hydrogenproduction.

Keywords

Hydrogen � Biomass � Pretreatments � Biohydrogenproduction � Limiting factors

1 Global Energy Demand

The global energy demand increased by 2.9% in 2018 andthe annual global energy consumption was estimated at13,864 million tons of oil equivalent (in 2018). Fossil fuelsare regarded as the major drivers of the industrial revolutionleading to economic and technological changes in the recentyears. In the total energy consumption, fossil fuel aloneaccounted 85% including oil (34%), natural gas (24%), andcoal (27%). Remaining 15% are used from other forms ofenergy such as nuclear energy (4%), hydroelectricity (7%),and renewable resources (4%) (BP 2019). The high con-sumption of fossil fuel in recent decades is considered as amajor factor for global warming. Also, the recent con-sumption trend indicates further growth in the increment ofgreenhouse gas emissions in future. In this context, over-coming the recent energy demand by lowering the emissionof greenhouse gas has become a great challenge.

Several researches are ongoing worldwide to discovercheaper, eco-friendly, and alternative renewable energysources which can minimize the world’s carbon footprint.Recent studies revealed that alternative and renewableenergy resources could be a better solution for sustainableenergy production and energy security in the future becausethey mitigate greenhouse gas emission (Sharif et al. 2019).Renewable and alternative energy resources are easilyavailable as compared to other energy sources and arederived from solar, hydropower, geothermal, wind, oceanresources, and solid biomass, and others (Ellabban et al.2014). Compared to other sources of renewable energies, theconversion of biomass for energy production is one of thecheapest and promising alternatives. Moreover, the biomassis readily and widely available and is cheap in terms ofinvestment costs and feasible technology (Macqueen andKorhaliller 2011).

J. R. Khatiwada � S. Shrestha � H. K. Sharma � W. Qin (&)Department of Biology, Lakehead University, 955 Oliver Road,Thunder Bay, ON P7B 5E1, Canadae-mail: [email protected]

H. K. SharmaDepartment of Biological Sciences, University of Alberta,Edmonton, AB T6G 2E9, Canada

© The Author(s), under exclusive license to Springer Nature Switzerland AG 2021Inamuddin and A. Khan (eds.), Sustainable Bioconversion of Waste to Value Added Products, Advances in Science,Technology & Innovation, https://doi.org/10.1007/978-3-030-61837-7_16

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Large quantity of bio-wastes is produced from differentsources including forestry, agriculture, industries, andhousehold solid waste in the world. These biomasses areconsidered as waste materials particularly in the developingcountries and creating several environmental issues (Chenet al. 2017; Worden et al. 2017). However, recent researcheshave indicated that they can be used as the energy sources tocontribute in the global energy production such as bioetha-nol, biohydrogen, methane, and other value-added products(Limayem and Ricke 2012; Xu et al. 2019; Keskin et al.2019). Therefore, this review provides recent progress andfindings on biohydrogen production from lignocellulosicbiomass with a special focus on hemicellulose and discussesthe techno-economic bottleneck involved in hydrogen pro-duction from plant biomass.

1.1 Classification of Energy Sources

1.1.1 Biomass and BiofuelsBiomass originates from biological materials (plants oranimals) that can be used in energy production. Lignocel-lulosic biomass is a reliable source of energy since the earlyage of human civilization. Fire is the major energy sourcefrom biomass and provides thermal energy to keep warmand be used for cooking food. There are several ways toproduce energy from biomass, for example, burning biomassto produce heat in thermal plants (to run the steam engineand generate electricity), and turning feedstocks into liquidbiofuels (ethanol) or biogas (hydrogen, oxygen, or methane)(Giampietro et al. 1997). Biofuels are fuel(s) either solid,liquid, or gaseous produced directly or indirectly from bio-mass (FAO 2004; Lee and Lavoie 2013). Biofuels aregrouped as first, second, and third-generation biofuels basedon the feedstock used and their technological innovation(Lee and Lavoie 2013).

1.1.2 First-Generation BiofuelsFirst-generation biofuels are derived from edible food likecorn, sugar, and vegetable oil (Aro 2016). Bioethanol is amajor by-product produced from the fermentation of ediblecrops like corn and sugars. Other feedstocks are widely usedto produce first-generation bioethanol including barley,potato, sugar-beets, and sugarcane. The first-generationbiofuels can blend with petroleum-based fuels and poten-tial improvement on exhaust emissions (Mancaruso et al.2011). Though the first-generation biofuels have significantpositive impacts on environmental pollution and carbonemission, it is not a sustainable energy production becausefood security versus fuels is its major challenge. Still, it isclaimed that biodiesel is not a cost-efficient emissionreduction technology. Therefore, more cost-efficient alter-native technologies are recommended.

1.1.3 Second-Generation BiofuelsSecond-generation biofuels are derived from lignocellulosicbiomass such as crop and forest residues, and municipalsolid wastes (Begum and Dahman 2015). These biofuels aremore sustainable because they are cheap and produced fromabundant non-food plant materials. However, their produc-tion methods are still quite expensive and have severaltechnical barriers during the bioconversion processes(Mancaruso et al. 2011).

1.1.4 Third-Generation BiofuelsThird-generation biofuels are produced by using algal bio-mass to manufacture diesel and gasoline (Neto et al. 2019).The microalgae (examples: Nannochloropsis granulate,Spirulina maxima) can provide different types of renewablebiofuel like methane, biodiesel, gasoline, biohydrogen,and jet fuel. Thus, algae can provide a promising sourceof future fuel and other valuable products (Chowdhury et al.2019).

2 Lignocellulosic Biomass

Lignocellulosic biomass is the most abundant plant materialand is inexpensive, eco-friendly, and abundant renewableresource. It can be used in biofuels, chemicals, and polymerproduction (Li et al. 2007). There are three major compo-nents of lignocellulosic biomass: cellulose (40–60%),hemicellulose (20–40%), and lignin (10–24%) (Sharma et al.2019). However, the composition of these three primarycomponents varies based on plant type, age, cultivation, andclimate conditions.

2.1 Cellulose

Cellulose is the most abundant and major structural com-ponent of the plant cell wall (Fig. 1). It is an organizedfibrous structure consisting of D-glucose subunits connectedby b-1,4 glycosidic bonds (Fengel and Wegener 1989; Pérezet al. 2002). This linkage in carbohydrate or polysaccharidemakes cellulose as a straight chain polymer (also called ascellulose microfibrils) (Pérez et al. 2002). The microfibrilstructure of cellulose is composed of alternating crystallineand amorphous regions (Fengel and Wegener 1989; Nandaet al. 2014). The amorphous form of cellulose is susceptibleto enzymatic decomposition (Kumar et al. 2009).

2.2 Hemicellulose

It is the second most abundant polysaccharide found in plantbiomass (Fig. 1). Hemicellulose is composed of short lateral

268 J. R. Khatiwada et al.

chains of different hexose and pentose sugars (such asxylose, mannose, galactose, rhamnose, and arabinose) anduronic acids (Lin et al. 2015). Glucuronoxylan and gluco-mannan are the principal components of hardwood andsoftwood hemicellulose, respectively (Pérez et al. 2002).

2.3 Lignin

Lignin is a complex, branched phenolic polymer containingthree phenylpropanolic monomers linked by carbon-carbonand aryl-ether bonds (Lu et al. 2017; Upton and Kasko2016). Lignin accounts for 30% of total organic carbonfound on Earth (Upton and Kasko 2016). It is an aromaticnatural polymer found in all terrestrial and some of theaquatic plants (Guragain et al. 2015). It acts as a potentiallyrenewable resource for energy and aromatic chemical pro-duction. The lignin provides structural support, imperme-ability, transport water and nutrients, and protection againstchemical and pathogen attack (Polo et al. 2020; Bonawitzand Chapple 2010).

3 Bioconversion of Lignocellulosic Biomass

Each year several tons of lignocellulosic wastes are producedfrom different sources including forestry and agriculturalbiomass, paper and food industries, and municipal solid waste

(Limayem and Ricke 2012; Dashtban et al. 2009). Eventoday, these biomasses are considered as waste materials indeveloping countries which are creating several environ-mental issues (Chen et al. 2017; Worden et al. 2017). How-ever, recent data suggested that lignocellulosic biomasses canbe successfully converted into biofuels (Putro et al. 2016).The global bioethanol production has dramatically increasedsince 2000 and reached up to 72.06 Billion Gallons per year in2017 (EIA 2020) (Fig. 2). More than 84% of the globalethanol fuel production (22.86 out of 27.06 Billions of

Fig. 1 Diagrammatic representation of the lignocellulosic biomass and the role of pretreatment in the bioconversion

Fig. 2 Biofuel production by countries from 2000 to 2017 (Datasource EIA (2020))

Bioconversion of Hemicelluloses into Hydrogen 269

Gallons) was concentrated in two countries, USA (15.8) andBrazil (7.06) in 2017 (EIA 2020) (Fig. 3).

4 Pretreatment

The lignocellulosic biomass has a property to resist againstchemicals and biological degradation (Polo et al. 2020). Thestructural complexity of the plant cell wall hinders the pre-treatment process (Fig. 1) (Jeoh et al. 2017). Pretreatment ofbiomass is an essential tool in the bioconversion processes inwhich the structure of cellulosic biomass is converted to bemore accessible for enzymatic and microbial digestion(Galbe and Zacchi 2012; Zheng et al. 2014). In this process,the complex structure of carbohydrate polymers is convertedinto fermentable sugars. Several studies have been carriedout for the enhancement of the digestibility process of lig-nocellulosic biomass for the efficient conversion ofbiopolymers to biofuel (ethanol, methane and, hydrogen)and other products (Sharma et al. 2019; Koupaie et al. 2019).The major goal of pretreatment is to disintegrate the ligno-cellulosic biomass into its three major components; cellu-lose, hemicellulose, and lignin. Broadly the pretreatmentmethods can be divided into physical, chemical, physico-chemical, and biological methods or their combinations(Table 1) (Xu et al. 2019; Sindhu et al. 2016).

5 Hydrogen as a Promising Source of Energy

Hydrogen is considered as a promising alternative source ofenergy. It can be generated from natural and bioresources(Jiang et al. 2019). It is a colorless, odorless, tasteless, andhighly abundant gas. Hydrogen is a clean and non-toxicrenewable energy (Hosseini and Wahid 2016). There hasbeen increasing demand for hydrogen in different sectors, forexample, in the production of chemicals, electronic devices,food industries, desulfurization of crude oil in oil refineries,and steel industries (Glenk and Reichelstein 2019; Nicitaet al. 2020). It is reported that about 95% of currenthydrogen production is based on fossil fuel (IRENA 2018;Thomas et al. 2018). The most common ways of hydrogenproduction are steam-methane reforming, non-catalytic par-tial oxidation of fossil fuels, hybrid form, and electrolysis(chlor-alkali) processes (Muradov 2017). However, thesemethods are highly cost-inefficient, requiring sophisticatedtechnology for storage and distribution. Therefore,researchers are struggling to find the renewable and envi-ronmentally friendly sources of hydrogen production. Con-sequently, they have successfully uncovered thebioconversion process of lignocellulosic biomass (Xu 2007)and solid wastes (Lay et al. 1999) into hydrogen in the recentdecades. In the initial stage of the conversion process, plantbiomass and organic wastes are converted into methane bythe application of chemical reactions and bacteria. Thenorganic matters are hydrolyzed and fermented into fattyacids, which are then converted into acetate and hydrogen.

Bioconversion of lignocellulosic biomass into hydrogenhas several positive impacts in sustainable energy produc-tion, global energy use, and maintaining a sustainableenvironment. Following significant advantages of producinghydrogen as an energy resource can be highlighted:

• Hydrogen is clean and produces water vapor after com-bustion (Stern 2018).

• The combustion of hydrogen is about 50% more efficientthan gasoline (Kim et al. 2018).

• Hydrogen gas has a higher energy yield (122 kJ/g)compared to other hydrocarbon fuels (Kapdan and Kargi2006).

• Hydrogen battery can be used as future power for auto-mobiles (T-Raissi and Block 2004).

• Hydrogen gas can be easily stored as a metal hydridesuch as magnesium hydride, sodium aluminum hydride,lithium aluminum hydride, palladium hydride, etc. (Jain2009).

Fig. 3 Biofuel production by countries in the year 2017 (Data sourceEIA (2020))


5.1 Thermochemical Routes for HydrogenProduction from Biomass

Broadly, there are two ways of hydrogen production fromlignocellulosic biomass: they are thermochemical and bio-chemical methods (Fig. 4). Biochemical methods requirestarch or sugar enriched feedstock whereas various ranges oflignocellulosic biomass can be utilized in thermochemicalmethods (Basu 2013). Moreover, thermochemical methodsare much energy and cost-efficient and faster compared tobiochemical routes. Thermochemical process uses heat fromvarious resources, such as natural gas, coal, or biomass toconvert the lignocellulosic biomass into hydrogen. There arethree types of thermochemical processes (1) Pyrolysis,(2) Liquefaction, and (3) Gasification. Three methods,feedstock used, condition, product yield, major advantages,and disadvantages are summarized in Table 2.

Table 1 Comparison ofpretreatment methods oflignocellulosic biomass

Pretreatment Functions References

Physical pretreatment

Milling Breaks down the structure of lignocellulosic biomass, sizereduction, decrease crystallinity of cellulose

Bai et al. (2018)

Pyrolysis Decomposition of cellulose into H2, CO, and other carbonresidues at high temperatures (>300 °C)

Al Arni (2018)

Microwave Breakdown of lignocellulose and increase the enzymatic process Liu et al. (2018)

Extrusion Disruptions of lignocellulose in high temperature (>300 °C) Wahid et al.(2015)

Ultrasonication Breakdown of the lignin layer and disrupt the amorphous cell He et al. (2017)

Chemical pretreatment

Acid Breakdown lignin and other polymers under high temperature Lloyd andWyman (2005)

Alkali Breakdown lignin and other polymers under high temperature Sun et al. (2016)

Ionic liquids Cations and anions help to solubilize the cellulose and lignin Swatloski et al.(2002)

Organosolv Separation of cellulose by dissolving most lignin andhemicellulose with or without addition of a catalyst

Yu et al. (2018)

Deep eutecticSolvents

Solubilize polysaccharides, accelerate cellulose extraction,nanofibrillation or nanocrystalization

Zdanowicz et al.(2018)

Physicochemical pretreatments

Steamexplosion

Hemicellulose degradation by the application of heat in the formof pressurized steam

Chen and Liu(2015)

CO2 explosion Disruption of hemicellulose and lignin, enhance enzymatichydrolysis

Morais et al.(2015)

Liquid hotwater

Hydrolyzes hemicellulose and breakdown of lignin at high watertemperature and pressure

Zhuang et al.(2016)

Biological pretreatments

Whole cell Breakdown of lignin Hammel andCullen (2008)

Enzymaticpretreatment

Enzymatic degradation of lignin Zámocký et al.(2014)

Fig. 4 Methods of hydrogen production from biomass


5.1.1 PyrolysisPyrolysis is the conversion of biomass or any carbonaceousfeedstocks in anaerobic condition to produce charcoal,bio-oil, and biogas at a pressure of 0.1–0.5 MPa and atemperature of 500–900 °C (Ni et al. 2006; Bičáková andStraka 2012). The major purpose of the pyrolysis is to breakdown the polymeric molecules into shorter molecular weightcompounds. Biomass pyrolysis is categorized into conven-tional (slow), vacuum, fast, and flash pyrolysis. The majordifferences between slow and fast pyrolysis are the heatingrates (time) and maximum reaction temperatures (Al 2018).The differences in time and temperature significantly affectproduction of biofuels and other products. Slow pyrolysisproduces primarily gas while fast pyrolysis generates biofuel(Brown et al. 2011; Demirbas 2016). Therefore, fast pyrol-ysis is cost, time, and energy efficient in the conversion ofbiomass. Pyrolytic decomposition of biomass can be illus-trated by the following equation (Eq. 1) (Demirbas 2016):

Biomass þ Energy ! H2 þ CO þ CO2 þ HC gases

þ Tar þ Char

ð1Þ

i. Fast pyrolysis

The biomass feedstock is heated rapidly in anoxic condition.There are three main products of fast pyrolysis: bio-oil, gas,and char. Tar (47.13%) is the major product of fast pyrolysisfollowed by char (28.33%), losses (13.21%), and gases(11.33%) respectively at 653 K (Al 2018). The major gases

include H2, CH4, CO, CO2, and other depending on thefeedstocks used for pyrolysis (Demirbas 2016).

ii. Slow pyrolysis

It is the conventional form of pyrolysis in which the pro-duction of charcoal or char is the major by-product. Theplant biomass is heated slowly in an anaerobic condition to arelatively low temperature (about 400 °C) over an extendedperiod (Basu 2013). According to Al Arni (2018) char(37.64%) is the major product of slow pyrolysis followed bytar (26.11%), gas (25.10%), and losses (11.15%) at 753 K.

iii. Flash pyrolysis

Flash pyrolysis is also called very fast pyrolysis. In thisprocess biomass is rapidly heated (above 1000 °C/s) in ananoxic condition. The main product of the flash pyrolysis isbiofuel (about 70–75% of biomass) with 15–25% of biocharresidues (Basu 2013).

5.1.2 GasificationIn comparison to the pyrolysis processes, the gasificationprocess aims to maximize the conversion of a solid biomassinto usable gases. The gasification process converts organicbiomass into hydrogen and other products without com-bustion. In this process, biomass is heated at high tempera-tures (>700 °C) provided with a regulated amount of oxygenand steam. This process produces carbon monoxide (CO),hydrogen (H2), and carbon dioxide (CO2) (Eq. 2) (Balat andKırtay 2010). Biomass gasification takes place in a complexchain of chemical reactions. Usually, this process is

Table 2 Summary of pretreatments of biomass via pyrolysis and gasification

Method Feedstock Processcondition

H2 yield Major advantages Majordisadvantage

References

Fast pyrolysis Forest pinewoodwaste

500–600 °C

117 g per kg of biomass Simple process Lower yieldof biofuel

Arregi et al.(2016)

Flash pyrolysis Rice husk andsawdust

800 and900 °C

0.267 Nm3/kg Easy handlingprocess

Lesseconomic

Sun et al.(2010)

Slow pyrolysis Cellulose fibersand lignin

600 °C Xylan—0.30%, Cellulose—0.08%, Lignin—0.33% ofbiomass

Low‐value energyproduct

Notprofitable

Giudicianniet al. (2013)

Air gasification Pine sawdust 870 °C High temperature favoredhigher H2 production

Low‐value energyproduct

Lower yieldof hydrogen

Lv et al.(2007)

Air andoxygen/steamgasification

Pine woodblocks

886 °C 30.51% of total gas produced Higher yield in lowenergyconsumption

Lv et al.(2007)

Supercriticalwatergasification

Sawdust andmunicipal solidwaste

375 °Cand22 MPa

0.12% of total biomass Simple process Highprocessingcosts

Castelloet al. (2017)


completed through the following stages: drying, pyrolysis,char, and tar gasification. Different types of biomass mate-rials such as waste wood, sawdust, and agricultural wastecan be used to produce hydrogen via gasification (Basu2013).

C6H12O6 + O2 + H2O ! CO + CO2 + H2 + other

ð2Þ

5.1.3 LiquefactionLiquefaction (hydrothermal liquefaction) is a process ofconversion of lignocellulosic biomass into bio-liquid at atemperature of 280–370 °C and pressure of 10–25 MPa inthe absence of oxygen (Gollakota et al. 2018). The majorgoal of this process is to break down the solid biopolymericstructure into liquid components (Elliott et al. 2015). Duringthe conversion process many complex reactions take placeand convert biomass into crude oil-like products (Behrendtet al. 2008). There are major two types of process mecha-nism based on the nature of feedstock namely dry feedstock(lignocellulose biomass) and wet feedstock (algal biomass)(Elliott et al. 2015). Lower hydrogen yield is the majorlimitation of this method.

5.2 Biological Routes for Hydrogen Production

There has been growing interest in bioconversion of wasteproducts and biomass to produce biofuels and biohydrogen.Biohydrogen production is considered as an eco-friendly andinexhaustible process than electrolysis, thermochemical, andelectrochemical processes (Kırtay 2011). In biological pro-cesses the feedstocks are catalyzed by microorganisms underatmospheric pressure and at an ambient temperature. Bio-hydrogen production methods are broadly categorized aslight-dependent and light-independent processes (Ding et al.2016). Light-dependent processes can be further classifiedinto direct biophotolysis, indirect biophotolysis, andphoto-fermentation. Light-independent processes are alsocalled dark fermentation (Table 3).

5.2.1 Direct BiophotolysisBiohydrogen production through biophotolysis is carried outby photosynthetic organisms such as microalgae andcyanobacteria (Eq. 3) (Eroglu and Melis 2011). In thisprocess, autotrophs decompose water into hydrogen andoxygen in the presence of sunlight.

2H2O Sun light ! 2H2 + O2 ð3Þ

Table 3 Review of biological hydrogen process and its prospects

Methods Organisms H2 production Advantages Disadvantages References

Directbiophotolysis

Cyanobacteria and algae 1.1 mmol/l-h •H2 productionfrom hydrolysis•Lignocellulosicbiomass assubstrateEasy to operate

•Low H2

production rate•Extremely lightdependent•Low conversionefficiency fromlightProduct containsCO2 or O2

Sun et al. (2019), Tamburicet al. (2011)

Indirectbiophotolysis

Cyanobacteria 0.0114 kg H2/kg biomass

•H2 productionfrom water andsunlight•Lignocellulosicbiomass assubstrate•Easy to operate

•Lowphotochemicalefficiency•O2 is inhibitoryto nitrogenase

Sveshnikov et al. (1997),Hallenbeck and Benemann(2002)

Photo-fermentation Photosynthetic bacteria 2.41 molH2/mol glucose

•Sunlight assource of energy•Lignocellulosicbiomass assubstrate

•Highly lightdependent•Low H2

production

Toledo-Alarcón et al.(2018), Ghirardi et al.(2000)

Dark fermentation Obligate or facultativeanaerobic fermentativebacteria

32mmol/Lglucose

•H2 can beproduced withoutlight•Wide spectrumwaste can be used

•Low H2 yield•Largeproduction ofby-product gases

Li and Fang (2007),Ghirardi et al. (2000)


The hydrolysis is carried out into two different photosyn-thesis stages: photosystem I (PSI) and photosystem II (PSII).In photosystem I (PSI), production of the reductant of CO2

taken place whereas in photosystem II (PSII) split water intoH2 andO2 (Bolatkhan et al. 2019). In direct photolysis, variousgreen algae (such as Chlamydomonas reinhardtii, Chloro-coccumlittorale,Chlorella fusca, Platymonassubcordiformis,Scenedesmus obliquusetc.) (Fan et al. 2016; Guan et al. 2004)and cyanobacteria (Anabaena cylindrical, Oscillatoria brevis,Nostocmuscorum, etc.) are widely used for hydrogen pro-duction (Das and Veziroglu 2008; Dutta et al. 2005).

Water is used as the primary feedstock in the directbiophotolysis method which is inexpensive and availableeverywhere. On the other side, hydrogen production isprohibited by the suppressive effect of oxygen as aby-product of photosynthesis and enzymatic catalysis whichis the major drawback of this method (Table 3) (Sun et al.2019). Moreover, this process yields less hydrogen andcost-inefficient in the industrial-scale production (Sakuraiand Masukawa 2007).

5.2.2 Indirect BiophotolysisIndirect biophotolysis is carried out in two steps: photo-synthesis and fermentation. Firstly, the synthesis of carbo-hydrates takes place under the light (Eq. 4). Secondly, thehydrogen is produced from carbohydrates via anaerobic darkfermentation (Eq. 5) (Hallenbeck and Benemann 2002;Kossalbayev et al. 2020).

6H2O + 6CO2 Sun light ! C6H12O6 + 6O2 ð4Þ

C6H12O6 þ 12H2OSun light ! 12H12 + 6CO2 ð5ÞCyanobacteria play a major role in the production of

hydrogen in indirect biophotolysis processes. It possessesmajor enzymes such as nitrogenase and hydrogenase whichhelped in metabolic functions for the hydrogen (Hallenbeckand Benemann 2002; Kossalbayev et al. 2020).

5.2.3 Photo-FermentationIn this process, lignocellulosic feedstocks are decomposedinto hydrogen and carbon dioxide by using photosyntheticmicroorganisms such as Rhodobacter sp. in the presence ofsunlight and organic acids. Photo-fermentation occurs underoxygen deficient condition with the optimal temperature of30–35 °C and pH 7.0 (Eq. 6) (Argun and Kargi 2011). Inthis process wide range of organic wastes such as fruits andvegetable wastes or other lignocellulosic wastes can be usedas substrate for the production of biohydrogen (Özgür et al.2010; Fascetti and Todini 1995).

CH3COOH + 2H2O Sun light ! 4H2 + 2CO2 ð6Þ

5.2.4 Dark FermentationDark fermentation is environmentally friendly and widelyused method for biohydrogen production from organicfeedstocks. This process is undertaken in a dark and anaer-obic environment in which anaerobic bacteria convertcarbohydrate-rich substrates into hydrogen (Toledo-Alarcónet al. 2018). This process is carried out by different groups ofbacteria such as Enteric and Clostridia sp. (Khanna and Das2013). In the dark fermentation, the first step is the glycol-ysis process in which glucose is fermented to pyruvate.Then, under the anaerobic environment, pyruvate is oxidizedto acetyl-CoA, CO2, and H2 (Li and Fang 2007). Comparedto other biological production methods, dark fermentationprocess is cost-effective, higher hydrogen production rate,and faster conversion efficiencies. This process can utilize awide range of organic feedstocks including municipalwastes, agriculture, and forest residues (Ghimire et al. 2015).

6 Metabolic Pathway of HydrogenProduction

Hydrogen can be produced via biophotolysis,photo-fermentation, and dark fermentation (Ding et al.2016). Although biophotolysis by green microalgae andcyanobacteria is a highly desirable process, the photo-chemical efficiency is low due to oxygen inhibition onhydrogenase (Oh et al. 2013). Microbial fermentation (in-cluding dark fermentation and photo-fermentation) could beone of the potential alternatives to produce biohydrogen.However, except for the glucose, lignocellulosic biomass hasnot been studied extensively for the hydrogen productiondue to structural complexity of plant biomass. Usually, apretreatment of lignocellulosic biomass is an essential stepbefore hydrolysis to convert a complex biopolymer intofermentable sugars (glucose and xylose). Hydrolysis ofcellulosic biomass is catalyzed by synergistic effect ofcellulase-endoglucanase, cellobiohydrolase, andb-glucosidase to form glucose, whereas the hemicellulosiccomponents are catalyzed by hemicellulolytic enzymes suchas endo-xylanase, exo-xylanase, and b-xylosidase to formxylose (Sharma et al. 2019). These sugars can be utilizedfurther in hydrogen production. However, the hydrolysis oflignocellulosic biomass often produces some inhibitorycompounds such as phenolic and other aromatic compounds,levulinic acid, aliphatic acids, and furan aldehydes, etc.which inhibit the microbial growth and hinder the down-stream processing of bioproducts (Jönsson et al. 2013;Jönsson and Martín 2016). Thus, a direct bioconversion(without pretreatment) of cellulosic and hemicellulosic bio-mass for hydrogen production is gaining popularity due to itsenvironmental and economic benefit. Some thermophilic


bacteria including Clostridium sp., Caldicellulosiruptorsaccharolyticus, Thermoanaerobacterium sp., Thermotoga-maritima sp. Pyrococcusfuriosus sp., etc. can producehydrogen directly from various plant polymers (Cao et al.2014; Ren et al. 2008; Willquist et al. 2011; Verhaart et al.2010). When grown in polymeric biomass, these bacteriautilize various hydrolytic enzymes and hydrogenases forhydrogen production (Oh et al. 2013). Based on the literaturereviewed (Rollin et al. 2015; Reginatto and Antônio 2015;Yu and Takahashi 2007), we reconstruct the potentialmetabolic pathways for hydrogen production (Fig. 5).Reginatto and Antônio (2015) outlined the hydrogen pro-duction through fermentation pathways using Escherichiacoli and Enterobacteriaceae and several enzymes viaEmbden–Meyerhof–Parnas (EMP) pathway to form pyru-vate. The pyruvate is further catalyzed by ferredoxin oxy-doreductase and converted into acetyl-CoA and then to

acetate with the release of hydrogen and carbon dioxideunder anaerobic conditions. The enzyme hydrogenase playsa key role at the final stage of hydrogen production. Rollinet al. (2015) proposed another hydrogen generation pathwayfrom lignocellulosic biomass in which bioconversion cellu-losic and hemicellulosic biomasses in hydrogen productionare resulted in formation of monomeric sugars—glucose andxylose produced after hydrolysis of plant biomass. Thesesugars are subjected to phosphorylation by the action ofpolyphosphate. The nicotinamide adenine dinucleotidephosphate (NADPH) is further catalyzed by dehydrogenasesand hydrogenase to produced hydrogen. Here the nonox-idative pentose phosphate pathway and partial glycolysispathways recycle the ribulose, 5-xylulose, and 5-phosphatesto glucose 6-phosphates that ultimately used in the produc-tion of hydrogen (Rollin et al. 2015).

Fig. 5 Major metabolic pathways of hydrogen biosynthesis fromlignocellulosic biomass (adopted and modified from Rollin et al.(2015)). The enzymes and pathways are in blue and red-colored text,

respectively. The dashed arrows indicate the multi-steps metabolicpathway. Few representative bacteria, fungi, and abbreviated enzymesare included in the figure legend


7 Factors Affecting Hydrogen Productionin Dark Fermentation

7.1 Feedstock

Organic feedstocks play a major role in the production ofbiohydrogen from dark fermentation methods. Glucose andsucrose rich feedstock are model substrates for biohydrogenproduction (Ghimire et al. 2015). Still, complex substratessuch as municipal solid waste, forestry and agriculturalbiomasses (such as dead wood, corn stalks, wheat straw, andrice straw) and wastages from food processing industries(e.g., cheese whey, oil mills, and animals dungs) have beenwidely used in dark fermentation process to producehydrogen (Keskin et al. 2019; Kargi et al. 2012; Moham-madi et al. 2011; Chen et al. 2012).

7.2 pH

pH is a major factor that regulates the enzymatic functionsthereby affecting the metabolic pathway of organisms toproduce hydrogen (Ghimire et al. 2015). In the dark fer-mentation process, several facultative organisms have beenused to produce hydrogen via glycolysis (Tao et al. 2007).This enzymatic pathway of the hydrogen production ishighly sensitive to the pH. Tao et al. (2007) reported thatmaximum hydrogen yield at medium pH level (pH = 6).Thus, pH level significantly affects the hydrogenase enzymeactivity. If the medium concentration becomes acidic, pHlevel gets reduced which directly shifts enzymatic metabo-lism towards the conversion of acid into alcohol. At thelower pH level, hydrogen yield decreases sharply due to theproduction of acidic metabolites such as carboxylic acid,acetic acid, and formic acid. Similarly, Zagrodnik andLaniecki (2015) reported the reduction of the production ofH2 with increasing pH level.

7.3 Temperature

Temperature regulates the bacterial growth, rate of biohy-drogen production, and microbial metabolisms in anaerobicfermentation processes. The selection of optimal temperatureand organisms used for the fermentation process depends onfeedstock types. Due to the complexities of the lignocellu-losic biomass, there is considerable variation in operatingtemperature. Thus, optimal temperature selection is impor-tant based on bacteria/organisms used during fermentation.Organisms (anaerobic bacteria) that have been used for darkfermentation are classified into different groups (such aspsychrophiles, mesophiles, thermophiles, extreme

thermophiles, and hyperthermophiles) based on the optimaltemperature in which particular organism perform highermicrobial activities and also accelerate the bioconversionrate of feedstocks (Levin et al. 2004; Alvarado-Cuevas et al.2015; Boileau et al. 2016). Among them, mesophilic con-dition (temperature range: 25–45 °C, e.g. Clostridium sac-charobutylicum) is the most favorable temperature range forthe fermentative biohydrogen production (Li and Fang2007). In contrast, thermophilic (45–65 °C) andextreme-thermophilic (65–80 °C) bacteria can performeffectively during fermentation of the diversified feedstocksuch as buffalo manure, cheese whey, and sludge (Ghimireet al. 2015; Verhaart et al. 2010; Pakarinen et al. 2008).However, biohydrogen production fromextreme-thermophilic conditions requires higher energyinput (Hallenbeck 2005).

7.4 Hydrogen Partial Pressure (HPP)

HPP is a pressure created by hydrogen gas inside the reactorsystem (Hawkes et al. 2007). When hydrogen started toaccumulate inside the reactor, the partial pressure ofhydrogen increases and subsequently decreases the produc-tion of hydrogen. Consequently, metabolic pathway ofhydrogen production shifts and starts to the accumulatedother byproducts such as ethanol, acetone, and lactic acid,(Ghimire et al. 2015; Hawkes et al. 2007). Lee et al. (2012)reported that reduction of the partial pressure during thehydrogen metabolism in dark fermentation increases theproduction of H2.

7.5 Hydraulic Retention Time

Hydraulic retention time (or fermentation time or hydraulicloading) is the average number of time (days) that a feed-stock remains in a storage unit (digester/bioreactor).Hydraulic retention time is calculated by dividing bioreactorvolume (gallons) by the feed volume (gal/day) (Kim et al.2013). Higher hydrogen production is highly correlated withshorter retention time (Zhang et al. 2013).

8 Conclusion

Lignocellulosic biomass has been extensively used for bio-hydrogen production. It consists of biopolymer componentssuch as cellulose, hemicellulose, and lignin. Glucose andxylose are the final products after the appropriate pretreat-ment of hemicellulose or lignocellulosic biomass. Differentpretreatment methods, for example, physical, chemical, and


biological have been employed to convert the complexstructure of carbohydrate polymers into fermentable sugars.Biological pretreatments of lignocellulosic feedstock are themost desirable methods compared to conventional pretreat-ment methods which are cost-inefficient and produce unde-sirable inhibitors. Among the different methods of hydrogenproduction, the biological route is cheaper and eco-friendly.Biological hydrogen production process is highly affected byseveral factors such as feedstock, pH, temperature, the par-tial pressure of hydrogen, and hydraulic retention time.Further improvement in genetic engineering and biotech-nologies are needed for more efficient and cost-effectivebiological pretreatment and low-cost conversion of hemi-cellulose into hydrogen and other value-added products.

Acknowledgments This work was supported by the Natural Sciencesand Engineering Research Council of Canada (RGPIN-2017-05366) toW. Q.

References

Al Arni S. (2018). Comparison of slow and fast pyrolysis forconverting biomass into fuel. Renewable Energy, 2018(124), 197–201. https://doi.org/10.1016/j.renene.2017.04.060.

Alvarado-Cuevas, Z. D., López-Hidalgo, A. M., Ordoñez, L. G.,Oceguera-Contreras, E., Ornelas-Salas, J. T., & De León-Rodrí-guez, A. (2015). Biohydrogen production using psychrophilicbacteria isolated from Antarctica. International Journal of Hydro-gen Energy, 40(24), 7586–7592. https://doi.org/10.1016/j.ijhydene.2014.10.063.

Argun, H., & Kargi, F. (2011). Bio-hydrogen production by differentoperational modes of dark and photo-fermentation: an overview.International Journal of Hydrogen Energy, 36(13), 7443–7459.

Aro, E. M. (2016). From first generation biofuels to advanced solarbiofuels. Ambio, 45(1), 24–31.

Arregi, A., Lopez, G., Amutio, M., Barbarias, I., Bilbao, J., & Olazar,M. (2016). Hydrogen production from biomass by continuous fastpyrolysis and in-line steam reforming. RSC Advances, 6(31),25975–25985.

Bai, X., Wang, G., Yu, Y., Wang, D., & Wang, Z. (2018). Changes inthe physicochemical structure and pyrolysis characteristics of wheatstraw after rod-milling pretreatment. Bioresource Technology, 2018(250), 770–776. https://doi.org/10.1016/j.biortech.2017.11.085.

Balat, H., & Kırtay, E. (2010). Hydrogen from biomass–presentscenario and future prospects. International Journal of HydrogenEnergy, 35(14), 7416–7426.

Basu, P. (2013). Biomass gasification and pyrolysis: Practical designand theory. Academic press.

Begum, S., & Dahman, Y. (2015). Enhanced biobutanol productionusing novel Clostridial fusants in simultaneous saccharification andfermentation of green renewable agriculture residues. Biofuels,Bioproducts and Biorefining, 9(5), 529–544. https://doi.org/10.1002/bbb.1564.

Behrendt, F., Neubauer, Y., Oevermann, M., Wilmes, B., & Zobel, N.(2008). Direct liquefaction of biomass. Chemical Engineering andTechnology, 31(5), 667–677.

Bičáková, O., & Straka, P. (2012). Production of hydrogen fromrenewable resources and its effectiveness. International Journal of

Hydrogen Energy, 37(16), 11563–11578. https://doi.org/10.1016/j.ijhydene.2012.05.047.

Boileau, C., Auria, R., Davidson, S., Casalot, L., Christen, P., Liebgott,P.-P., et al. (2016). Hydrogen production by the hyperthermophilicbacterium Thermotoga maritima part I: Effects of sulfurednutriments, with thiosulfate as model, on hydrogen productionand growth. Biotechnology for Biofuels, 9(1), 269. https://doi.org/10.1186/s13068-016-0678-8.

Bolatkhan, K., Kossalbayev, B. D., Zayadan, B. K., Tomo, T.,Veziroglu, T. N., & Allakhverdiev, S. I. (2019). Hydrogenproduction from phototrophic microorganisms: Reality and per-spectives. International Journal of Hydrogen Energy, 44(12),5799–5811. https://doi.org/10.1016/j.ijhydene.2019.01.092.

Bonawitz, N. D., & Chapple, C. (2010). The genetics of ligninbiosynthesis: Connecting genotype to phenotype. Annual Review ofGenetics, 2010(44), 337–363.

BP. (2019) BP statistical review of world energy. London, UK.Brown, T. R., Wright, M. M., & Brown, R. C. (2011). Estimating

profitability of two biochar production scenarios: Slow pyrolysis vsfast pyrolysis. Biofuels, Bioproducts and Biorefining, 5(1), 54–68.https://doi.org/10.1002/bbb.254.

Cao, G.-L., Zhao, L., Wang, A.-J., Wang, Z.-Y., & Ren, N.-Q. (2014).Single-step bioconversion of lignocellulose to hydrogen using novelmoderately thermophilic bacteria. Biotechnology for Biofuels, 7(1), 82.

Castello, D., Rolli, B., Kruse, A., & Fiori, L. (2017). Supercritical watergasification of biomass in a ceramic reactor: Long-time batchexperiments. Energies, 10(11), 1734.

Chen, H. Z., & Liu, Z. H. (2015). Steam explosion and itscombinatorial pretreatment refining technology of plant biomassto bio-based products. Biotechnology Journal, 10(6), 866–885.

Chen, C.-C., Chuang, Y.-S., Lin, C.-Y., Lay, C.-H., & Sen, B. (2012).Thermophilic dark fermentation of untreated rice straw using mixedcultures for hydrogen production. International Journal of Hydro-gen Energy, 37(20), 15540–15546.

Chen, J., Li, C., Ristovski, Z., Milic, A., Gu, Y., Islam, M. S., et al.(2017). A review of biomass burning: Emissions and impacts on airquality, health and climate in China. Science of the TotalEnvironment, 2017(579), 1000–1034.

Chowdhury, H., Loganathan, B., Mustary, I., Alam, F., & Mobin, S. M.(2019). Algae for biofuels: The third generation of feedstock. In A.Basile & F. Dalena (Eds.), Second and third generation offeedstocks (pp. 323–344). Rende, Italy: Elsevier.

Das, D., & Veziroglu, T. N. (2008). Advances in biological hydrogenproduction processes. International Journal of Hydrogen Energy,33(21), 6046–6057.

Dashtban, M., Schraft, H., & Qin, W. (2009). Fungal bioconversion oflignocellulosic residues; opportunities & perspectives. InternationalJournal of Biological Sciences, 5(6), 578–595. https://doi.org/10.7150/ijbs.5.578.

Demirbas, A. (2016). Comparison of thermochemical conversionprocesses of biomass to hydrogen-rich gas mixtures. EnergySources, Part A: Recovery, Utilization, and Environmental Effects,38(20), 2971–2976. https://doi.org/10.1080/15567036.2015.1122686.

Ding, C., Yang, K. L., & He, J. (2016). Biological and fermentativeproduction of hydrogen. In R. Luque, C S. K. Lin, K. Wilson,J. (Eds.), Handbook of biofuels production (2nd ed) (303–333).Woodhead Publishing.

Dutta, D., De, D., Chaudhuri, S., & Bhattacharya, S. K. (2005).Hydrogen production by Cyanobacteria.Microbial Cell Factories, 4(1), 36. https://doi.org/10.1186/1475-2859-4-36.

EIA. (2020) Global Ethanol Production: Quantity of ethanol produced bycountry from 2007 to 2017. The U.S. Energy Information Admin-istration (EIA), Washington DC, USA. Accessed 21 April 2020.


Ellabban, O., Abu-Rub, H., & Blaabjerg, F. (2014). Renewable energyresources: Current status, future prospects and their enablingtechnology. Jouranl of Renewable Sustainable Energy Reviews,2014(39), 748–764.

Elliott, D. C., Biller, P., Ross, A. B., Schmidt, A. J., & Jones, S. B.(2015). Hydrothermal liquefaction of biomass: Developments frombatch to continuous process. Bioresource Technology, 2015(178),147–156. https://doi.org/10.1016/j.biortech.2014.09.132.

Eroglu, E., & Melis, A. (2011). Photobiological hydrogen production:Recent advances and state of the art. Bioresource Technology, 102(18), 8403–8413.

Fan, X., Wang, H., Guo, R., Yang, D., Zhang, Y., Yuan, X., et al.(2016). Comparative study of the oxygen tolerance of Chlorellapyrenoidosa and Chlamydomonas reinhardtii CC124 in photobio-logical hydrogen production. Algal Research, 16, 240–244.

FAO. Unified Bioenergy Terminology UBET. Rome, Italy: Food andAgriculture Organisation of the United Nations (FAO)2004 Con-tract No.: 12 April 2020.

Fascetti, E., & Todini, O. (1995). Rhodobacter sphaeroides RVcultivation and hydrogen production in a one-and two-stagechemostat. Applied Microbiology and Biotechnology, 44(3–4),300–305.

Fengel, D., & Wegener, G. (1989). Wood: Chemistry, ultrastructure,reactions. Berlin, Germany: Walter de Gruyter.

Galbe, M., & Zacchi, G. (2012). Pretreatment: The key to efficientutilization of lignocellulosic materials. Biomass and Bioenergy,2012(46), 70–78. https://doi.org/10.1016/j.biombioe.2012.03.026.

Ghimire, A., Frunzo, L., Pontoni, L., d’Antonio, G., Lens, P. N.,Esposito, G., et al. (2015a). Dark fermentation of complex wastebiomass for biohydrogen production by pretreated thermophilicanaerobic digestate. Journal of Environmental Management, 2015(152), 43–48.

Ghimire, A., Frunzo, L., Pirozzi, F., Trably, E., Escudie, R., Lens,P. N., et al. (2015b). A review on dark fermentative biohydrogenproduction from organic biomass: Process parameters and use ofby-products. Applied Energy, 2015(144), 73–95.

Ghirardi, M. L., Zhang, L., Lee, J. W., Flynn, T., Seibert, M.,Greenbaum, E., et al. (2000). Microalgae: A green source ofrenewable H2. Trends in Biotechnology, 18(12), 506–511.

Giampietro, M., Ulgiati, S., & Pimentel, D. (1997). Feasibility oflarge-scale biofuel production. BioScience, 47(9), 587–600.

Giudicianni, P., Cardone, G., & Ragucci, R. (2013). Cellulose,hemicellulose and lignin slow steam pyrolysis: Thermal decompo-sition of biomass components mixtures. Journal of Analytical andApplied Pyrolysis, 2013(100), 213–222. https://doi.org/10.1016/j.jaap.2012.12.026.

Glenk, G., & Reichelstein, S. (2019). Economics of convertingrenewable power to hydrogen. Nat Energ., 4(3), 216–222.

Gollakota, A. R. K., Kishore, N., & Gu, S. (2018). A review onhydrothermal liquefaction of biomass. Renewable and SustainableEnergy Reviews, 2018(81), 1378–1392. https://doi.org/10.1016/j.rser.2017.05.178.

Guan, Y., Deng, M., Yu, X., & Zhang, W. (2004). Two-stagephoto-biological production of hydrogen by marine green algaPlatymonas subcordiformis. Biochemical Engineering Journal, 19(1), 69–73.

Guragain, Y. N, Herrera, A. I., Vadlani, P. V., Prakash, O. (2015).Lignins of bioenergy crops: A review. Natural Product Commu-nications 10(1), 1934578X1501000141.

Hallenbeck, P. (2005). Fundamentals of the fermentative production ofhydrogen. Water Science and Technology, 52(1–2), 21–29.

Hallenbeck, P. C., & Benemann, J. R. (2002). Biological hydrogenproduction; fundamentals and limiting processes. InternationalJournal of Hydrogen Energy, 27(11–12), 1185–1193.

Hammel, K. E., & Cullen, D. (2008). Role of fungal peroxidases inbiological ligninolysis. Current Opinion in Plant Biology, 11(3),349–355. https://doi.org/10.1016/j.pbi.2008.02.003.

Hawkes, F. R., Hussy, I., Kyazze, G., Dinsdale, R., & Hawkes, D. L.(2007). Continuous dark fermentative hydrogen production bymesophilic microflora: Principles and progress. International Jour-nal of Hydrogen Energy, 32(2), 172–184.

He, Z., Wang, Z., Zhao, Z., Yi, S., Mu, J., & Wang, X. (2017).Influence of ultrasound pretreatment on wood physiochemicalstructure. Ultrasonics Sonochemistry, 2017(34), 136–141.

Hosseini, S. E., & Wahid, M. A. (2016). Hydrogen production fromrenewable and sustainable energy resources: Promising greenenergy carrier for clean development. Renewable and SustainableEnergy Reviews, 2016(57), 850–866. https://doi.org/10.1016/j.rser.2015.12.112.

IRENA. (2018). Hydrogen from renewable power: Technology outlookfor the energy transition. Abu Dhabi: International RenewableEnergy Agency (IRENA).

Jain, I. (2009). Hydrogen the fuel for 21st century. InternationalJournal of Hydrogen Energy, 34(17), 7368–7378.

Jeoh, T., Cardona, M. J., Karuna, N., Mudinoor, A. R., & Nill,J. (2017). Mechanistic kinetic models of enzymatic cellulosehydrolysis—a review. Biotechnology and Bioengineering, 114(7),1369–1385.

Jiang, Y., Lu, J., Lv, Y., Wu, R., Dong, W., Zhou, J. et al. (2019).Efficient hydrogen production from lignocellulosic feedstocks by anewly isolated thermophlic Thermoanaerobacterium sp. strain F6.International Journal of Hydrogen Energy 44(28), 14380–6. https://doi.org/10.1016/j.ijhydene.2019.01.226.

Jönsson, L. J., & Martín, C. (2016). Pretreatment of lignocellulose:Formation of inhibitory by-products and strategies for minimizingtheir effects. Bioresource Technology, 2016(199), 103–112.

Jönsson, L. J., Alriksson, B., & Nilvebrant, N.-O. (2013). Bioconver-sion of lignocellulose: inhibitors and detoxification. Biotechnologyfor Biofuels, 6(1), 16.

Kapdan, I. K., & Kargi, F. (2006). Bio-hydrogen production from wastematerials. Enyzme and Microbial Technology, 38(5), 569–582.

Kargi, F., Eren, N. S., & Ozmihci, S. (2012). Hydrogen gas productionfrom cheese whey powder (CWP) solution by thermophilic darkfermentation. International Journal of Hydrogen Energy, 37(3),2260–2266.

Keskin, T., Abubackar, H. N., Arslan, K., Azbar, N. (2019).Biohydrogen production from solid wastes. In A. Pandey, S.V. Mohan, J.-S.Chang, P. C. Hallenbeck, C. Larroche (Eds.),Biohydrogen (pp. 321–46). Elsevier.

Khanna, N., & Das, D. (2013). Biohydrogen production by darkfermentation. Wires Energy & Environment, 2(4), 401–421. https://doi.org/10.1002/wene.15.

Kim, M.-S., Cha, J., & Kim, D.-H. (2013). Chapter 11-Fermentativebiohydrogen production from solid wastes. In A. Pandey, J.-S.Chang, P. C. Hallenbecka, & C. Larroche (Eds.), Biohydrogen(pp. 259–283). Amsterdam: Elsevier.

Kim, J., Chun, K. M., Song, S., Baek, H.-K., & Lee, S. W. (2018).Hydrogen effects on the combustion stability, performance andemissions of a turbo gasoline direct injection engine in variousair/fuel ratios. Applied Energy, 2018(228), 1353–1361.

Kırtay, E. (2011). Recent advances in production of hydrogen frombiomass. Energy Conversion and Management, 52(4), 1778–1789.https://doi.org/10.1016/j.enconman.2010.11.010.

Kossalbayev, B. D., Tomo, T., Zayadan, B. K., Sadvakasova, A. K.,Bolatkhan, K., Alwasel, S., et al. (2020). Determination of thepotential of cyanobacterial strains for hydrogen production. Inter-national Journal of Hydrogen Energy, 45(4), 2627–2639. https://doi.org/10.1016/j.ijhydene.2019.11.164.


Koupaie, E. H., Dahadha, S., Lakeh, A. B., Azizi, A., & Elbeshbishy,E. (2019). Enzymatic pretreatment of lignocellulosic biomass forenhanced biomethane production-a review. Journal of Environ-mental Management, 2019(233), 774–784.

Kumar, P., Barrett, D. M., Delwiche, M. J., & Stroeve, P. (2009).Methods for pretreatment of lignocellulosic biomass for efficienthydrolysis and biofuel production. Industrial and EngineeringChemistry Research, 48(8), 3713–3729.

Lay, J.-J., Lee, Y.-J., & Noike, T. (1999). Feasibility of biologicalhydrogen production from organic fraction of municipal solidwaste.Water Research, 33(11), 2579–2586. https://doi.org/10.1016/S0043-1354(98)00483-7.

Lee, R. A., & Lavoie, J.-M. (2013). From first-to third-generationbiofuels: Challenges of producing a commodity from a biomass ofincreasing complexity. Animal Frontiers, 3(2), 6–11.

Lee, K.-S., Tseng, T.-S., Liu, Y.-W., & Hsiao, Y.-D. (2012). Enhancingthe performance of dark fermentative hydrogen production using areduced pressure fermentation strategy. International Journal ofHydrogen Energy, 37(20), 15556–15562.

Levin, D. B., Pitt, L., & Love, M. (2004). Biohydrogen production:prospects and limitations to practical application. InternationalJournal of Hydrogen Energy, 29(2), 173–185.

Li, C., & Fang, H. H. (2007). Fermentative hydrogen production fromwastewater and solid wastes by mixed cultures. Critical Reviews inEnvironmental Science and Technology, 37(1), 1–39.

Li, A., Antizar-Ladislao, B., & Khraisheh, M. (2007). Bioconversion ofmunicipal solid waste to glucose for bio-ethanol production.Bioprocess and Biosystems Engineering, 30(3), 189–196. https://doi.org/10.1007/s00449-007-0114-3.

Limayem, A., & Ricke, S. C. (2012). Lignocellulosic biomass forbioethanol production: Current perspectives, potential issues andfuture prospects. Progress in Energy and Combustion Science, 38(4), 449–467.

Lin, D., Lopez-Sanchez, P., & Gidley, M. J. (2015). Binding ofarabinan or galactan during cellulose synthesis is extensive andreversible. Carbohydrate Polymers, 2015(126), 108–121. https://doi.org/10.1016/j.carbpol.2015.03.048.

Liu, Y., Sun, B., Zheng, X., Yu, L., & Li, J. (2018). Integratedmicrowave and alkaline treatment for the separation betweenhemicelluloses and cellulose from cellulosic fibers. BioresourceTechnology, 2018(247), 859–863.

Lloyd, T. A., & Wyman, C. E. (2005). Combined sugar yields for dilutesulfuric acid pretreatment of corn stover followed by enzymatichydrolysis of the remaining solids. Bioresource Technology, 96(18),1967–1977.

Lu, Y., Lu, Y.-C., Hu, H.-Q., Xie, F.-J., Wei, X.-Y., & Fan, X. (2017).Structural characterization of lignin and its degradation productswith spectroscopic methods. Journal of Spectroscopy, 2017, 1–15.

Lv, P., Yuan, Z., Ma, L., Wu, C., Chen, Y., & Zhu, J. (2007).Hydrogen-rich gas production from biomass air and oxygen/steamgasification in a downdraft gasifier. Renewable Energy, 32(13),2173–2185. https://doi.org/10.1016/j.renene.2006.11.010.

Macqueen, D., & Korhaliller, S. (2011) Bundles of energy: The case forrenewable biomass energy. Natural Resources Issue, Vol. 24.London: IIED.

Mancaruso, E., Sequino, L., & Vaglieco, B. M. (2011). First andsecond generation biodiesels spray characterization in a dieselengine. Fuel, 90(9), 2870–2883. https://doi.org/10.1016/j.fuel.2011.04.028.

Mohammadi, P., Ibrahim, S., Annuar, M. S. M., & Law, S. (2011).Effects of different pretreatment methods on anaerobic mixedmicroflora for hydrogen production and COD reduction from palmoil mill effluent. Journal of Cleaner Production, 19(14), 1654–1658.

Morais, A. R., da Costa Lopes, A. M., & Bogel-Łukasik, R. (2015).Carbon dioxide in biomass processing: contributions to the greenbiorefinery concept. Chemical Reviews, 115(1), 3–27.

Muradov, N. (2017). Low to near-zero CO2 production of hydrogenfrom fossil fuels: Status and perspectives. International Journal ofHydrogen Energy, 42(20), 14058–14088.

Nanda, S., Mohammad, J., Reddy, S. N., Kozinski, J. A., & Dalai, A.K. (2014). Pathways of lignocellulosic biomass conversion torenewable fuels. Biomass Conversion and Biorefinery, 4(2), 157–191.

Neto, J. M., Komesu, A., da Silva Martins, L. H., Gonçalves, V. O. O.,de Oliveira, J. A. R., Rai, M. (2019). Chapter 10-Third generationbiofuels: an overview. In M Rai, A. P. Ingle (Eds.), SustainableBioenergy (pp. 283–98). Elsevier.

Ni, M., Leung, D. Y. C., Leung, M. K. H., & Sumathy, K. (2006). Anoverview of hydrogen production from biomass. Fuel ProcessingTechnology, 87(5), 461–472. https://doi.org/10.1016/j.fuproc.2005.11.003.

Nicita, A., Maggio, G., Andaloro, A. P. F., & Squadrito, G. (2020).Green hydrogen as feedstock: Financial analysis of aphotovoltaic-powered electrolysis plant. International Journal ofHydrogen Energy, 45(20), 11395–11408. https://doi.org/10.1016/j.ijhydene.2020.02.062.

Oh, Y.-K., Raj, S. M., Jung, G. Y., & Park, S. (2013). Metabolicengineering of microorganisms for biohydrogen production. Bio-hydrogen (pp. 45–65). Elsevier.

Özgür, E., Mars, A. E., Peksel, B., Louwerse, A., Yücel, M., Gündüz,U., et al. (2010). Biohydrogen production from beet molasses bysequential dark and photofermentation. International Journal ofHydrogen Energy, 35(2), 511–517.

Pakarinen, O., Lehtomäki, A., & Rintala, J. (2008). Batch darkfermentative hydrogen production from grass silage: The effect ofinoculum, pH, temperature and VS ratio. International Journal ofHydrogen Energy, 33(2), 594–601.

Pérez, J., Munoz-Dorado, J., De la Rubia, T., & Martinez, J. (2002).Biodegradation and biological treatments of cellulose, hemicellu-lose and lignin: An overview. International microbiology, 5(2), 53–63.

Polo, C. C., Pereira, L., Mazzafera, P., Flores-Borges, D. N., Mayer,J. L., Guizar-Sicairos, M., et al. (2020). Correlations between lignincontent and structural robustness in plants revealed by X-rayptychography. Scientific Reports, 10(1), 1–11.

Putro, J. N., Soetaredjo, F. E., Lin, S.-Y., Ju, Y.-H., & Ismadji, S.(2016). Pretreatment and conversion of lignocellulose biomass intovaluable chemicals. RSC Advances, 6(52), 46834–46852.

Reginatto, V., & Antônio, R. V. (2015). Fermentative hydrogenproduction from agroindustrial lignocellulosic substrates. BrazilianJournal of Microbiology, 46(2), 323–335.

Ren, N., Cao, G., Wang, A., Lee, D.-J., Guo, W., & Zhu, Y. (2008).Dark fermentation of xylose and glucose mix using isolatedThermoanaerobacterium thermosaccharolyticum W16. Interna-tional Journal of Hydrogen Energy, 33(21), 6124–6132.

Rollin, J. A., del Campo, J. M., Myung, S., Sun, F., You, C., Bakovic,A., et al. (2015). High-yield hydrogen production from biomass byin vitro metabolic engineering: mixed sugars coutilization andkinetic modeling. Proceedings of the National Academy of Sciences,112(16), 4964–4969.

Sakurai, H., & Masukawa, H. (2007). Promoting R & D inphotobiological hydrogen production utilizing mariculture-raisedcyanobacteria. Marine Biotechnology, 9(2), 128–145.

Sharif, A., Raza, S. A., Ozturk, I., & Afshan, S. (2019). The dynamicrelationship of renewable and nonrenewable energy consumptionwith carbon emission: A global study with the application ofheterogeneous panel estimations. Renewable Energy, 133, 685–691.


Sharma, H. K., Xu, C., & Qin, W. (2019). Biological pretreatment oflignocellulosic biomass for biofuels and bioproducts: An overview.Waste and Biomass Valorization, 10(2), 235–251.

Sindhu, R., Binod, P., & Pandey, A. (2016). Biological pretreatment oflignocellulosic biomass–An overview. Bioresource Technology,2016(199), 76–82. https://doi.org/10.1016/j.biortech.2015.08.030.

Stern, A. G. (2018). A new sustainable hydrogen clean energyparadigm. International Journal of Hydrogen Energy, 43(9), 4244–4255.

Sun, S., Tian, H., Zhao, Y., Sun, R., & Zhou, H. (2010). Experimentaland numerical study of biomass flash pyrolysis in an entrained flowreactor. Bioresource Technology, 101(10), 3678–3684. https://doi.org/10.1016/j.biortech.2009.12.092.

Sun, S., Sun, S., Cao, X., & Sun, R. (2016). The role of pretreatment inimproving the enzymatic hydrolysis of lignocellulosic materials.Bioresource Technology, 2016(199), 49–58.

Sun, Y., He, J., Yang, G., Sun, G., & Sage, V. (2019). A review of theenhancement of bio-hydrogen generation by chemicals addition.Catalysts, 9(4), 353.

Sveshnikov, D., Sveshnikova, N., Rao, K., & Hall, D. (1997).Hydrogen metabolism of mutant forms of Anabaena variabilis incontinuous cultures and under nutritional stress. FEMS Microbiol-ogy Letters, 147(2), 297–301.

Swatloski, R. P., Spear, S. K., Holbrey, J. D., & Rogers, R. D. (2002).Dissolution of cellose with ionic liquids. Journal of the AmericanChemical Society, 124(18), 4974–4975.

Tamburic, B., Zemichael, F. W., Maitland, G. C., & Hellgardt, K.(2011). Parameters affecting the growth and hydrogen production ofthe green alga Chlamydomonas reinhardtii. International Journal ofHydrogen Energy, 36(13), 7872–7876.

Tao, Y., Chen, Y., Wu, Y., He, Y., & Zhou, Z. (2007). High hydrogenyield from a two-step process of dark- and photo-fermentation ofsucrose. International Journal of Hydrogen Energy, 32(2), 200–206. https://doi.org/10.1016/j.ijhydene.2006.06.034.

Thomas, H., Armstrong, F., Brandon, N., David, B., Barron, A.,Durrant, J., et al. (2018). Options for producing low-carbonhydrogen at scale. London: The Royal Society.

Toledo-Alarcón, J., Capson-Tojo, G., Marone, A., Paillet, F., Júnior, A.D. N. F., & Chatellard, L. et al. (2018). Basics of bio-hydrogenproduction by dark fermentation. In Q Liao, J. -S. Chang, CHerrmann, A Xia (Eds.), Bioreactors for Microbial Biomass andEnergy Conversion (pp. 199–220). Singapore: Springer Singapore.

T-Raissi, A., Block, D. L. (2004). Hydrogen: Automotive fuel of thefuture. IEEE Power and Energy Magazine 2(6), 40–5.

Upton, B. M., & Kasko, A. M. (2016). Strategies for the conversion oflignin to high-value polymeric materials: Review and perspective.Chemical Reviews, 116(4), 2275–2306.

Verhaart, M. R., Bielen, A. A., Oost, J. V. D., Stams, A. J., & Kengen,S. W. (2010) Hydrogen production by hyperthermophilic andextremely thermophilic bacteria and archaea: Mechanisms forreductant disposal. Environmental Technology 31(8–9), 993–1003.

Wahid, R., Hjorth, M., Kristensen, S., & Møller, H. B. (2015).Extrusion as pretreatment for boosting methane production: Effectof screw configurations. Energy & Fuels, 29(7), 4030–4037.

Willquist, K., Pawar, S. S., & Van Niel, E. W. (2011). Reassessment ofhydrogen tolerance in Caldicellulosiruptor saccharolyticus. Micro-bial Cell Factories, 10(1), 111.

Worden, J. R., Bloom, A. A., Pandey, S., Jiang, Z., Worden, H. M.,Walker, T. W., et al. (2017). Reduced biomass burning emissionsreconcile conflicting estimates of the post-2006 atmosphericmethane budget. Nature Communications, 8(1), 2227.

Xu, Z. (2007). Chapter 21-Biological Production of Hydrogen fromRenewable Resources. In S.-T. Yang (Ed.), Bioprocessing forvalue-added products from renewable resources (pp. 527–557).Amsterdam: Elsevier.

Xu, N., Liu, S., Xin, F., Zhou, J., Jia, H., Xu, J., et al. (2019).Biomethane production from lignocellulose: Biomass recalcitranceand its impacts on anaerobic digestion. Frontiers in Bioengineeringand Biotechnology, 7(191), 1–12. https://doi.org/10.3389/fbioe.2019.00191.

Yu, J., & Takahashi, P. (2007) Biophotolysis-based hydrogen produc-tion by cyanobacteria and green microalgae. In A. M. Vilas (Ed.),Communicating current research and educational topics and trendsin applied microbiology. Formatex (pp. 79–89).

Yu, H.-T., Chen, B.-Y., Li, B.-Y., Tseng, M.-C., Han, C.-C., & Shyu,S.-G. (2018). Efficient pretreatment of lignocellulosic biomass withhigh recovery of solid lignin and fermentable sugars using Fentonreaction in a mixed solvent. Biotechnology for Biofuels, 11(1), 287.

Zagrodnik, R., & Laniecki, M. (2015). The role of pH control onbiohydrogen production by single stage hybrid dark-andphoto-fermentation. Bioresource Technology, 194, 187–195.https://doi.org/10.1016/j.biortech.2015.07.028.

Zámocký, M., Gasselhuber, B., Furtmüller, P. G., & Obinger, C.(2014). Turning points in the evolution of peroxidase–catalasesuperfamily: molecular phylogeny of hybrid heme peroxidases.Cellular and Molecular Life Sciences, 71(23), 4681–4696. https://doi.org/10.1007/s00018-014-1643-y.

Zdanowicz, M., Wilpiszewska, K., & Spychaj, T. (2018). Deep eutecticsolvents for polysaccharides processing. A review. CarbohydratePolymers, 200, 361–380. https://doi.org/10.1016/j.carbpol.2018.07.078.

Zhang, F., Ge, Z., Grimaud, J., Hurst, J., & He, Z. (2013). Long-termperformance of liter-scale microbial fuel cells treating primaryeffluent installed in a municipal wastewater treatment facility.Environmental Science & Technology, 47(9), 4941–4948.

Zheng, Y., Zhao, J., Xu, F., & Li, Y. (2014). Pretreatment oflignocellulosic biomass for enhanced biogas production. Progressin Energy and Combustion Science, 2014(42), 35–53. https://doi.org/10.1016/j.pecs.2014.01.001.

Zhuang, X., Wang, W., Yu, Q., Qi, W., Wang, Q., Tan, X., et al.(2016). Liquid hot water pretreatment of lignocellulosic biomass forbioethanol production accompanying with high valuable products.Bioresource Technology, 199, 68–75.


Bioconversion of Hemicelluloses into Hydrogen

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